Rhodium containing selective catalysts for the synthesis of epoxysiloxane/epoxysilicone monomers and polymers

ABSTRACT

The invention provides a method for making a curable epoxysilicone composition through the hydrosilation reaction between an ethylenically unsaturated epoxide and an SiH-containing silicone to produce an epoxysilicone product, and catalyzed by a rhodium containing selective catalyst which does not promote the oxirane ring-opening reaction of either the ethylenically unsaturated epoxide starting material or the epoxysilicone product. The invention also provides for a curable epoxysilicone composition made by the above method for the catalyst, and two methods of making the catalyst.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is related to copending applications Attn. Dock. No.60SI-1502, Attn. Dock. No. 60SI-1418, and previously filed pendingapplication Ser. Nos. 07/583,524, 07/473,802, and 07/802,679 the entiredisclosures of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a method of producing epoxysilicones viarhodium-based catalysts which promote a hydrosilation addition reactionbetween an ethylenically unsaturated epoxide and an organohydrogensilaneor organohydrogensiloxane, without also promoting the oxiranering-opening polymerization of the ethylenically unsaturated epoxidestarting material or the epoxysilicone hydrosilation reaction product.The invention also relates to a curable epoxysilicone composition madeby the present method.

2. Technology Review

In the production of epoxysilicone compositions, transition metalcatalysts have long been known to promote the hydrosilation reaction.See, for example, J. L. Speier, "Homogeneous Catalysis of Hydrosilationby Transition Metals" in Advances in Organometallic Chemistry, Vol. 17,pp. 407-447, F. G. A. Stone and R. West, eds., Academic Press (New York,San Francisco, London), 1979; Aylett, Organometallic Compounds, Vol. 1,p. 107, John Wiley & Sons (New York), 1979; and Crivello and Lee, "TheSynthesis, Characterization, and Photoinitiated Cationic Polymerizationof Silicon-Containing Epoxy Resins", J. Polymer Sci., Vol 28, pp.479-503, John Wiley & Sons (New York), 1990. Generally, thehydrosilation catalysts used are complexes of platinum, palladium,rhodium, iridium, iron or cobalt. In particular, platinum-containingcatalysts have been widely used for this purpose.

The most commonly used platinum-containing hydrosilation catalysts arethose derived from chloroplatinic acid. These catalysts tend to beunstable and to form metal cluster compounds or colloids (Cotton andWilkenson, in Advanced Inorganic Chemistry, 4th edit., John Wiley andSons (New York), 1980). Chloroplatinic acid itself is both thermally andphotochemically unstable in solution. In addition, its composition isvariable depending on its state of hydration. For example,chloroplatinic acid typically contains the H₃ O⁺, H₅ O₂ ⁺, and H₇ O₃ ⁺ions. On standing in solution at room temperature, chloroplatinic acidwill oftentimes deposit elemental platinum. On thermal decomposition,volatile Pt₆ Cl₁₂ is also formed as one of the intermediates (Schweizerand Kerr, "Thermal Decomposition of Hexachloroplatinic Acid" inInorganic Chemistry, vol. 17, pp. 2326-2327, 1978).

It has been found that in addition to catalyzing the hydrosilationreaction, many transition-metal-complex catalysts in the presence ofsilicon hydrides also promote the oxirane ring-opening polymerization ofthe ethylenically unsaturated epoxide starting material and theepoxysilicone product of the hydrosilation reaction. Reference is made,for example, to copending, commonly assigned application Ser. No.07/473,802 (Riding, et al.), filed Feb. 2, 1990, which discloses the useof platinum or platinum-based catalysts to promote the oxiranering-opening polymerization of epoxides. This ring-openingpolymerization reaction during production of an epoxysilicone isundesirable as the epoxide polymerization may cause the reaction mixtureto gel completely, resulting in the loss of the entire batch and in lossof considerable time in cleanup of the insoluble gelled resin.

Additionally, a partial gelation due to the ring-opening polymerizationreaction can occur during epoxysilicone synthesis such that reproduciblebatch-to-batch viscosity of the epoxysilicone product is difficult toobtain. Such reproducibility in viscosity is highly preferred in theepoxysilicone industry, as these materials are typically used ascoatings, for example release coatings, and the process of successfullyand uniformly applying these coatings to a substrate is highly dependentupon the viscosity of the coating material. Commonly assigned, copendingapplications to Eckberg, et al., Attorney Docket No. 60SI-1466 and60SI-1492, both filed Dec. 5, 1991, disclose that viscosity control canbe achieved by use of a tertiary amine stabilizer during thehydrosilation synthesis reaction. However, only a limited number oftransition-metal hydrosilation catalysts are active in the presence ofthis stabilizer.

In the presence of precious metal hydrosilation catalysts,epoxysilicones have been found to slowly gel on storage at roomtemperature due to the epoxide ring-opening polymerization reaction,thus shortening the shelf-life of the epoxysilicone product. While thisstorage problem can be partially alleviated by deactivating thetransition-metal-complex catalyst with an inhibitor of its catalyticactivity, such as dodecyl mercaptan or 2-mercaptobenzothiazole in thecase of platinum complexes, it would be preferable to not incorporatethis extra component and additional process step into epoxysiliconecomposition and production process.

In most of the catalytic systems involving platinum complexes, thecatalytic species is not well understood. Recently, colloids have beenshown to be the active species involved in some of catalytichydrosilation reactions (Lewis, Journal of the American ChemicalSociety, vol. 112, p. 5998, 1990) and in the ring-opening polymerizationof epoxides ("Novel Platinum Containing Initiators for Ring-OpeningPolymerizations", Journal of Polymer Science, Pt. A; Polymer ChemistryEdition, Vol. 25, 1853-1863, 1991.) Other reports suggest that thecatalytic species in the hydrosilation reaction is a non-colloidal metalcomplex (See, for example, Harrod and Chalk, in Organic Synthesis ViaMetal Carbonyls, p. 673, Wender and Pino, eds., John Wiley & Sons (NewYork), 1977).

In order to minimize the oxirane ring-opening polymerization reaction,epoxysilicone fluids have been previously successfully produced only bycareful control of batch temperature and olefin epoxide feed rate duringthe synthesis, followed by the above-mentioned inactivation of thecatalyst after the completion of the hydrosilation reaction.

As disclosed in commonly assigned U.S. patent application of Crivelloand Fan, entitled "Preparation of Epoxysilicon Compounds using RhodiumCatalysts", attorney docket 60SI-1374, certain rhodium-basedhydrosilation catalysts selectively promote the hydrosilation reactionwithout the promotion of an epoxide ring-opening polymerizationreaction. A variety of epoxy-containing silicone monomers and oligomerscan be synthesized using these catalysts. However, most of the catalyststraditionally used for synthesis of epoxysilicone compositions,particularly Pt-containing catalysts, promote the epoxide ring-openingpolymerization reaction, and therefore do not permit the selectivehydrosilation synthesis of epoxysilicones.

The use of certain quaternary onium hexachloroplatinates as catalyst forthe hydrosilation reaction between phenylacetylene and triethylsilanehas been previously described. Reference is made to Iovel, I., Goldberg,Y., Shymanska, M. and Lukevics, E., in Organometallics, vol. 6, pp.1410-1413, 1987. However, this study did not indicate the suitability ofthe quaternary onium hexachloroplatinates as useful hydrosilationcatalysts for addition to vinyl epoxides, nor did it suggest that suchsalts effectively suppress the catalyst-dependent ring-openingpolymerization of epoxy groups in either the starting ethylenicallyunsaturated epoxide or the epoxysilicone product of the hydrosilationreaction.

In consideration of the above, it is apparent that there exists a needin the epoxysilicone industry for a method of eliminating the oxiranering-opening when employing commonly used hydrosilation catalysts. Therealso exists a need for an efficient yet economical method of producingepoxysilicone monomers and oligomers in the absence of the epoxidering-opening side reaction, thereby generating epoxysiliconecompositions of reproducible batch-to-batch viscosity. There isadditionally a need for epoxysilicone composition which is stable to theepoxide ring-opening reaction and, therefore, has an increasedshelf-life without the additional step and cost of poisoning thecatalyst after the completion of the hydrosilation addition reaction.

SUMMARY OF THE INVENTION

The present invention provides a method for making an epoxy-containingorganosilicone compound, comprising the steps of:

(i) preparing the mixture comprising an ethylenically unsaturatedepoxide (A) , an organohydrogensilane or organohydrogensiloxane (B) anda quaternary ammonium or phosphonium rhodium halide (C); and

(ii) reacting the mixture of said step (i), under conditions whichpromote a hydrosilation addition reaction between (A) and (B) to producean epoxysilicone product, and which do not promote an epoxidering-opening reaction in either (A) or in said epoxysilicone product.

The invention also provides for the novel rhodium selective catalyst(C), two methods of making the novel rhodium catalyst (C), and a curableepoxysilicone composition derived from Components (A), (B) and (C).

Thus, it is an object of the present invention to provide a method forpreparing an epoxysilicone composition through the reaction between anethylenically unsaturated epoxide and an organohydrogensilane ororganohydrogensiloxane in the presence of a catalyst which efficientlypromotes the hydrosilation reaction without also promoting theafore-mentioned oxirane ring-opening polymerization of either theethylenically unsaturated epoxide starting material or the epoxysiliconeproduct.

It is another object of the invention to provide a hydrosilationcatalyst for the addition reaction between an olefin epoxide and aSiH-containing silane or siloxane to form an epoxysilicone compound,wherein the catalyst effectively promotes the hydrosilation reactionwithout also promoting the ring-opening polymerization of the epoxidering in either the olefin epoxide starting material or the epoxysiliconeproduct.

Still another object of the invention is to provide two methods ofmaking the hydrosilation catalyst for the addition reaction between anolefin epoxide and a SiH-containing silane or siloxane to form anepoxysilicone compound, wherein the catalyst effectively promotes thehydrosilation reaction without also promoting the ring-openingpolymerization of the epoxide ring in either the olefin epoxide startingmaterial or the epoxysilicone product.

Still another object of the invention is to provide a curableepoxysilicone composition with reproducible batch-to-batch viscosity andenhanced storage life, and which is stable to oxirane ring-openingpolymerization at room temperature.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is based on the unexpected discovery thatquaternary onium rhodium halides are effective for promoting theaddition of ethylenically unsaturated epoxides to silicon hydrideswithout also promoting the oxirane ring-opening polymerization reactionof the epoxide starting material or the epoxysilicone final product.

Although not intending the present invention to be limited by themechanism of operation of the quaternary salt in increasing thespecificity of a rhodium halide catalyst for the hydrosilation reaction,it is believed that the onium salt stabilizes the active catalyticrhodium species, and prevents the formation of colloidal rhodium.

The present invention provides a method for making an epoxy-containingorganosilicone compound, comprising the steps of:

(i) preparing the mixture comprising:

(A) from about 1 to about 20 parts by weight of the composition of anethylenically unsaturated epoxide;

(B) from about 0.5 to about 400 parts by weight of the composition of anorganohydrogensiloxane or an organohydrogensilane; based on (A) and

(C) from about 1 to about 5000 parts per million by weight as comparedto the weight of the composition of a hydrosilation catalyst of theformula

    [R.sub.4 M].sup.+ [RhCl.sub.3 Br].sup.-

wherein M is phosphorous or nitrogen and R is an organic radicalcomprising C_(1-18') substituted or unsubstituted, linear alkyl radical,or an aryl, alkaryl or aralkyl radical; and

(ii) reacting the mixture of said step (i), under conditions whichpromote a hydrosilation addition reaction between (A) and (B) to producean epoxysilicone product, and which do not promote an epoxidering-opening reaction in either (A) or in said epoxysilicone product.

The invention also provides for the novel rhodium selective catalyst(C), two methods of making the novel rhodium catalyst (C), and a methodof using the composition derived from Components (A), (B) and (C).

By not promoting the oxirane ring-opening polymerization reaction thehydrosilation catalyst (C) allows highly reactive, curableepoxysilicones with improved viscosity control and without the danger ofgelation during or after synthesis. Such curable epoxysilicones areuseful in the production of, for example, silicone paper release agents,decorative and protective coatings, ink, adhesives, electronicsencapsulants and insulation and other uses of epoxysiloxanes.

Component (A) used in the method and composition of the presentinvention is an ethylenically unsaturated, i.e., either vinyl- orallyl-functional, epoxide. The ethylenically unsaturated epoxides usefulin Component (A) generally include any aliphatic (glycidyl) orcycloaliphatic epoxy compounds having olefinic moieties which willreadily undergo the hydrosilation addition reaction toorganohydrogensilicone compounds of Component (B). Commerciallyavailable examples of such ethylenically unsaturated epoxides useful inthe practice of the invention include allyl glycidyl ether; methallylglycidyl ether; 1-methyl-4-isopropenyl cyclohexene oxide;2,6-dimethyl-2,3-epoxy-7-octene; 1,4-dimethyl-4-vinylcyclohexene oxide;4-vinylcyclohexene oxide; vinylnorbornene monoxide; dicyclopentadienemonoxide. Other suitable examples of useful ethylenically unsaturatedepoxides include 1,2-epoxy-6-heptene, 1,2-epoxy-3-butene and chemicallysimilar, unsaturated aliphatic, cycloaliphatic, and alkylaromaticepoxides.

The preferred ethylenically unsaturated epoxide is 4-vinylcyclohexeneoxide.

Component (A) is used in the method and composition of the presentinvention in an amount ranging from about 1 to about 20 parts by weightof the composition, preferably from about 1 to about 10 parts by weightof the composition, and most preferably from about 1 to about 5 parts byweight of the composition.

Component (B) is an organohydrogensiloxane or organohydrogensilane.Suitable silicon hydride-containing starting materials generally includeany silicon compound derived from a silane or at least twoorganosiloxane units having terminal and/or pendant SiH groups. TheSiH-containing silicones useful in the practice of the invention arethose capable of reacting with the ethylenically unsaturated moieties ofthe epoxides of Component (A) above via the hydrosilation additionreaction.

Component (B) may be either a linear hydrogen substituted polysiloxaneor silane or a cyclic hydrogen substituted polysiloxane or silane, or acombination of the two. The linear hydrogen substituted polysiloxane orsilane may be either branched or unbranched. In addition, Component (B)organohydrogensiloxanes useful in the invention may be copolymers,terpolymers, etc. Illustrative Examples of such copolymers are apoly(dimethyl siloxane)-poly(methylhydrogen siloxane) copolymer or, whenUV cure in conjunction with onium salt catalysts is desired in thecurable composition of the present invention, apolyether/hydrogensiloxane linear block copolymer, such as described incopending, commonly assigned U.S. patent application of Eckberg, et al.,Attorney Docket 60SI-1466, filed Dec. 5, 1991).

Representative examples of suitable linear SiH-containing compoundsinclude 1,1,3,3-tetraalkyldisiloxane, dialkylhydrogensiloxy-endstoppedpolydialkylsiloxane, copolymer comprising at least twoalkylhydrogensiloxane groups, (e.g., (CH₃)₂ (H)SiO[(CH₃)₂ SiO]_(x)[(CH₃)(H)SiO]_(y) --Si(H)(CH₃)₂, where x and y are greater than or equalto 1). Other examples of SiH-containing compounds useful in theinvention include 1,1,3,3-tetramethyldisiloxane,2,4,6,8-tetramethyl-cyclotetrasiloxane, methyldimethoxysilane,triethylsilane, and methyldiethoxysilane. Other examples includecompounds of the formulae:

    (CH.sub.3).sub.2 HSiO[(CF.sub.3 CH.sub.2 CH.sub.2)(CH.sub.3)SiO].sub.m --[(CH.sub.3).sub.2 SiO].sub.n --Si(H)(CH.sub.3).sub.2

where m and n are integers and n is from about 4 to about 5000 and m isfrom about 3 to about 20.

The preferred linear SiH-containing silicon compound for Component (B)in the present invention is 1,1,3,3-tetramethyldisiloxane. Thepreferable cyclic hydride polysiloxane is2,4,6,8-tetramethylcyclotetrasiloxane.

The preferred Component (B) in the present invention is theaforementioned 1,1,3,3-tetramethyldisiloxane.

Component (B) is used in the method and composition of the presentinvention in an amount ranging from about 0.5 to about 400 parts byweight of the composition, preferably from about 1 to about 200 parts byweight of the composition, and most preferably from about 1 to about 100parts by weight of the composition based on the weight of Component (A).

Component (C) of the present invention comprises a quaternary oniumrhodium halide hydrosilation catalyst of the formula

    [R.sub.4 M].sup.+ [RhCl.sub.3 Br].sup.-

wherein M is phosphorous or nitrogen, and R is an organic radicalcomprising C_(1-18') substituted or unsubstituted, linear alkyl, or anaryl, alkaryl or aralkyl radical.

The R substituents of Component (C) may be the same or different in anygiven complex and may be, for example, methyl, ethyl, n-butyl, hexyl,stearyl, phenyl, tolyl, and benzyl. By the term "substituted" it ismeant an organic radical having chloro, bromo, iodo, cyano, carboxy,mercapto, hydroxy, thio, amino, nitro, phospho or other functionalgroups as known in the art. Moreover, heterocyclic and aromaticheterocyclic organic radicals such as pyridyl, thiophenyl, pyranyl, andthe like as known in the art are also meant to be encompassed in thedefinition of "substituted" organic radicals. The R substituents mayalso represent R¹ ₃ SiQ-- groups in which Q represents a divalentaliphatic hydrocarbon radical having from 1 to 6, inclusive, carbonatoms, for example, --CH₂ --, --CH₂ CH₂ --, and --CH₂ CHCH₃ CH₂ -- andeach R¹ represents an alkyl, aryl, aralkyl, or alkaryl radical asdefined and exemplified for R, above, or one R¹ substituent mayrepresent a trimethylsilyl radical.

The following examples are meant to be illustrative of suitablequaternary onium rhodium halide hydrosilation catalysts useful in thepractice of the invention:

    [(n-C.sub.4 H.sub.9).sub.4 N].sup.+ [RhCl.sub.3 Br].sup.- ; [(n-C.sub.4 H.sub.9).sub.4 P].sup.+ [RhCl.sub.3 Br].sup.- ;

    [(n-C.sub.18 H.sub.37).sub.4 N].sup.+ [RhCl.sub.3 Br].sup.- ; and [(n-C.sub.7 H.sub.15).sub.4 N].sup.+ [RhCl.sub.3 Br].sup.-

The preferred hydrosilation catalyst in the practice of the invention istetra-n-butylammonium rhodium trichloride bromide.

In addition to the high degree of selectivity of the catalysts ofComponent (C) described in this invention, these catalysts of Component(C) have further benefits over those previously available. For example,the catalysts are very stable and do not undergo deactivation during usein the presence of oxygen. This appears due to oxidation of thetriphenylphosphine residues to triphenylphosphine oxide which does notcoordinate well to the rhodium metal center. In the present catalysts,the quaternary ammonium and phosphonium ligands are not succeptable tooxidation and are, therefore, more stable under the reaction conditions.Further, the catalysts are very soluble in the reaction medium and canbe used particularly in cases in which the substrate is a poor solventwith a low dielectric constant. Lastly, the catalysts of the presentinvention are less expensive than traditional hydrosilation catalystssuch as Wilkinson's catalyst. This is because triphenylphosphine used tomake this catalyst is expensive as compared to quaternary ammonium andphosphonium halides. Secondly, the new catalysts are obtained in highyields, whereas the yields of Wilkinson's catalyst are generally low andthe catalyst requires extra separation and purification steps.

Component (C), the quaternary onium rhodium halide catalyst may beprepared one of two methods. One method involves producing a rhodiumcontaining selective catalyst (C) for the synthesis ofepoxysiloxane/epoxysilane monomers and polymers by first preparing amixture of a hydrate of a rhodium halide with the general formula,

    RhX.sub.3.mH.sub.2 O

where X is chlorine or bromine and m is from about 1 to about 10,preferably from about 2 to about 4, and most preferably from about 3 toabout 4, which is then dissolved in water; together with a quaternaryonium halide dissolved in a suitable organic solvent with the generalformula,

    R.sub.4 M.sup.+ X.sup.-

where X is chlorine or bromine, and M is nitrogen or phosphorus. Thismixture is then mixed. Mixing is important because it affects thereactivity of the onium salts with the rhodium salts. Mixing can beaccomplished using any means that one skilled in the art would normallyutilize for mixing two immiscible fluids. After mixing, the organiclayer is separated from the water. The rhodium containing selectivecatalyst is then removed by drying or evaporation from the organicsolvent. The means and methods for mixing, separating and drying orevaporation are well known in the art and are too numerous to list inthis application. The following examples are used by way of illustrationand not by way of limitation. An example of a means of separating thewater from the organic is by using a desiccant which preferably is CaCl₂; and a means for evaporating or drying are respectively a rotaryevaporator or by heating the mixture from about 25° to about 100° C.over a suitable period of time.

The other method of producing a rhodium containing selective catalyst(C) for the synthesis of epoxysiloxane/epoxysilane monomers and polymersis by mixing a hydrate of a rhodium halide with the general formula,

    RhX.sub.3.mH.sub.2 O

where X is chlorine or bromine and m is from about 1 to about 10,preferably from about 2 to about 4, and most preferably from about 3 toabout 4; together with a quaternary onium halide with the generalformula,

    R.sub.4 M.sup.+ X.sup.-

where X is chlorine or bromine, and M is nitrogen or phosphorus; andthen mixing this combination with an organic solvent. This mixture isthen mixed. Mixing is again important because it affects the reactivityof the onium salts with the rhodium salts. Mixing can be accomplishedusing any means that one skilled in the art would normally utilize formixing two immiscible fluids. The solution with the rhodium containingselective catalyst can be used either directly or can be dried orevaporated and can then be used. The means and methods for mixing, anddrying or evaporation are well known in the art and are too numerous tolist in this application. The following examples are used by way ofillustration and not by way of limitation. An example of a means ofevaporating or drying are respectively a rotary evaporator or by heatingthe mixture from about 25° to about 100° C. over a suitable period oftime.

In the method and composition of the present invention the catalysts (C)are most useful and economical in the range of from about 1 to about5000 parts per million of the weight of the composition of purecatalyst, preferably from about 5 to about 100 parts per million of theweight of the composition, and most preferably from about 5 to about 10parts per million of the weight of the composition, based upon theweight of the composition consisting of Components (A), (B) and (C).

To practice the method and make the curable composition of the presentinvention, Components (A), (B) and (C) are brought together in areaction vessel of suitable size for the size of the batch. Addition ofthe Components is preferably with mixing. A volatile solvent, preferablytoluene, xylene or hexane, may also be added to the reaction mixture inorder to facilitate the mixing process and dispersion of the components.

The curable epoxysilicone composition of the invention is then preparedby reacting the mixture of Components (A), (B) and (C) at a temperaturein the range of from about 0° C. to about 200° C., preferably from about25° C. to about 150° C. and most preferably from about 60° C. to about120° C. The temperature of the reaction mixture is then maintained untilthe completion of the addition reaction, which can be convenientlydetermined through IR spectroscopy by the disappearance of the strongabsorbance at 2200 cm⁻¹ due to the SiH group.

A preferred curable composition of the present invention comprises a(cyclohexene oxide)ethyl silane or a (cyclohexene oxide)ethyl siloxane.

In one embodiment of the invention, the present composition is readilyprepared by mixing Components (A), (B), and (C) either in a reactionvessel or otherwise. In another embodiment of the invention, any two ofComponents (A), (B) or (C), as defined above, can be pre-mixed, and thethird Component then added later to produce the composition of theinvention by the present method. Such mixtures in this embodimentexemplify the fact that the Components of the invention may be pre-mixedso as to provide what is in practicing the invention essentially atwo-component system for making a curable epoxysilicone.

After the completion of the hydrosilation reaction any volatile solventpreviously added can be removed from the composition of the inventionthrough evaporation, preferably at elevated temperature and reducedpressure.

The temperature at which the composition devolitilizes (i.e., where thesolvent is driven off) may be between from about 0° C. to about 200° C.,preferably between from about 25° C. and about 150° C. and mostpreferably between from about 60° C. to about 120° C. If a tertiaryamine stabilizer is incorporated into the practice of the presentinvention, then the temperature of devolitization may be between fromabout 0° C. to about 150° C., preferably between about 25° C. and about120° C., and most preferably between from about 50° C. and 100° C.

The pressure of the stripping step is generally preferred to be belowatmospheric, as such reduced pressure aids in the release of volatilemolecules from the composition of the invention. Preferably thestripping step is at less than 25 torr and most preferably at less than10 torr.

The stripping of volatile molecules, including unreacted volatileComponents and low molecular weight side products of the hydrosilationreaction, may be conveniently achieved through use of a rotaryevaporator, thin film evaporator, wiped film evaporator or the like.

The curable composition of the invention can be applied to cellulosicand other substrates including paper, metal, foil, polyethylene-coatedpaper (PEK), supercalendered paper, polyethylene films, polypropylenefilms and polyester films. In general, coatings can be applied to thesesubstrates at the desired thickness. For example, the composition of theinvention is readily applicable by doctor blade. For applications as arelease coating, the composition of the invention is applied at athickness of between about 0.1 mil and about 10 mils; it is alsoconvenient to refer to such coatings in terms of coat weights, typicallyabout 1 g/m².

The application and dispersion of the curable composition of theinvention onto a substrate may be facilitated if the composition isadded as a solution or dispersion in a volatile liquid carrier in whichthe epoxysilicone composition is soluble. When the curable compositionis a polydimethylsiloxane, preferable volatile liquid carriers include,for example, hexane, xylene or toluene. It should be recognized,however, that when the curable composition of the invention is acopolymer, terpolymer, etc., the volatile solvent must be chosen suchthat the polymer is soluble in the solvent, which may depend upon theparticular physical and chemical properties of the polymer as recognizedin the art. The amount of volatile liquid carrier incorporated into thecomposition should not exceed about 3% by weight as compared to thetotal weight of the curable composition, if the advantages of using arelatively solvent-free composition are desired.

Curing of the composition of the invention can be either thermally or,in the presence of the appropriate photocatalyst and possibly cureaccelerator, through UV irradiation. It has been found that the presenceof the quaternary onium halorhodium complex of the composition of theinvention does not substantially interfere with either of these curingmethods.

Polymerization by heat involves the simple step of heating theepoxysilicones to a temperature of about 120° C. or greater, whichcauses the oxirane ring to open and thereby react. Reference is made inthis regard to Pleudemann and Fanger, "Epoxyorganosiloxanes", Journal ofthe American Chemical Society, Vol. 81, pp. 2632-2635, 1959.

Polymerization by UV radiation involves the use of a photocatalyst that,when irradiated with UV light, forms an acid that catalyzes thecrosslinking of epoxysilicone monomers through the epoxide ring-openingreaction. Such reactions are disclosed, for example, in U.S. Pat. No.4,279,717 (Eckberg) and U.S. Pat. No. 4,617,238. Preparation ofphotoinitator salts useful for epoxysilicone polymerization aredisclosed, for example, in Crivello and Lee, "Alkoxy-SubstitutedDiaryliodonium Salt Cationic Photoinitiators", Journal of PolymerScience, Part A: Polymer Chemistry, Vol. 27, John Wiley, New York 1989,pp. 3951-3968.

Cure performance of the composition of the invention and adhesion of theepoxysilicone product may be enhanced by the addition of epoxidemonomers to the composition of the invention after the hydrosilationreaction is completed. For example, addition of up to 10 parts of analiphatic epoxide monomer for every 10 parts epoxysilicone may result incomposition exhibiting superior UV cured and anchorage on porouscellulose paper as compared to similar compositions without these"reactive diluents".

In order that persons skilled in the art may better understand thepractice of the present invention, the following examples are providedby way-- of illustration, and not by way of limitation. Additionalinformation which may be useful in state-of-the-art practice may befound in each of the references and patents cited herein, which arehereby incorporated by reference.

EXAMPLES Example 1 Preparation of [(n-C₄ H₉)₄ N]⁺ [RhCl₃ Br]--

The following synthesis is typical of that employed for the preparationof all of the modified rhodium catalysts described in this disclosure.

Combined together were 0.05 g of rhodium trichloride hydrate dissolvedin 30 mL of water and 0.10 g of tetra-n-butylammonium bromide dissolvedin 20 mL methylene chloride. The mixture was stirred for 3 hours at roomtemperature. After this time, the purple-red methylene chloride layerwas separated and dried over CaCl₂ for 5 hours. A red powder (the activecatalyst) was obtained after removing the solvent on a rotaryevaporator.

Example 2 Preparation of [(n-C₄ H₉)₄ P]⁺ [RhCl₃ Br]--

Employing the procedure described in example 1, 0.10 g of RhCl₃.xH₂ O in100 mL water and 0.16 g of (C₄ H₉)₄ P⁺ Br⁻ dissolved in 100 mL methylenechloride were combined. After work up as described above, the desiredcatalyst,[(n-C₄ H₉)₄ P]⁺ [RhCl₃ Br]--, was isolated as a light redcolored powder.

Example 3 Ring-Opening Polymerization of Cyclohexene Oxide

There were mixed together in a small vial, 1.0 g of cyclohexene oxideand 1.0 g of 1,1,3,3-tetramethyldisiloxane and 5 mg of RhCl₃.nH₃ O. TheRhCl₃.nH₃ O was very poorly soluble, however, after standing for oneweek, the reaction became visibly viscous. Analysis of the reactionmixture by gel permeation chromatography showed high molecular weight,polymeric products to be present. The experiment was repeated using[(n-C₄ H₉)₄ N]⁺ [RhCl₃ Br]⁻⁻. Under the same conditions, nopolymerization of the epoxide was observed.

Example 4 Selective Hydrosilylations

Into a 50 mL round bottom flask equipped with a magnetic stirrer and areflux condenser were added 2.0 g of 4-vinylcyclohexene oxide, 1.0 g of1,1,3,3-tetramethyldisiloxane and 5 mg of [(n-C₄ H₉)₄ N]⁺ [RhCl₃ Br].After standing for 24 hours at room temperature, the diepoxide shownbelow was obtained. ##STR1##

Example 5

Example 4 was repeated replacing the catalyst with [(n-C₄ H₉)₄ P]⁺[RhCl₃ Br]--. The reaction mixture was heated at 80°-90° C. for 6 hours.Again, only the diepoxide product was observed without evidence ofpolymer formation.

Example 6

Example 4 was again repeated using [(n-C₁₈ H₃₇)₄ N]⁺ [RhCl₃ Br]13 as thecatalyst. In this case also, pure ##STR2## was obtained in quantitativeyield without evidence of polymer formation.

Example 7 Comparison Between Onium Salts of Rhodium, Iridium, andRuthenium

Various onium salts (Q⁺ X⁻) were compared for the selectivity forhydrosilation over ring opening polymerization employing the followingreaction. ##STR3##

Into 1 100 mL round bottom flask were placed 2.0 g of 4-vinylcyclohexeneoxide, 1.08 g of 1,1,3,3-tetramethyldisiloxane. The flask was equippedwith a reflux condenser and a magnetic stirrer and the flask was placedinto an oil bath heated at 80°-90° C. The results of these experimentsare shown in following Table.

                  TABLE                                                           ______________________________________                                        Comparison of Various Transition Metal Onium                                  Salts.                                                                        O.sup.+ X.sup.-                                                                             Time (hr)  Results                                              ______________________________________                                        [(C.sub.4 H.sub.9).sub.4 N].sup.+ [RhCl.sub.3 Br].sup.-                                     1          Only diepoxide                                                                (quantitative conversion)                            [(C.sub.4 H.sub.9).sub.4 N].sup.+ [IrCl.sub.3 Br].sup.-                                     9          Crosslinked polymer                                  [(C.sub.6 H.sub.5).sub.4 As].sup.+ [RhCl.sub.4 ].sup.-                                      1.5        Crosslinked polymer                                  [(C.sub.4 H.sub.9).sub.4 N].sup.+ [RuCl.sub.3 Br].sup.-                                     9          Trace diepoxide                                      [(C.sub.4 H.sub.9).sub.4 N].sup.+ [RuCl.sub.3 Br].sup.-                                     20         Mainly starting material                                                      polymer and diepoxide.                               ______________________________________                                    

Example 8

A. 0.40 g of Aliquat 336 (a commercial oily product from Henkel, MeN(C₈H₁₇)₃ Cl, 0.10 g of RhCl₃.nH2O were reacted together in 4.0 mL tolueneunder stirring at 85° C. for 3 hours. A dark brown solution was obtainedand used directly as a selective hydrosilation catalyst.

B. The above catalyst was tested for selectivity. 5 Drops of thecatalyst and 0.1 mL of phenylsilane were mixed with 1.0 g of cyclohexeneoxide. The resulting solution was yellow, however, no reaction wasobserved. This result was confirmed by GPC analysis.

C. 3 Drops of the catalyst were introduced into a reaction mixtureconsisting of 4.0 g 4-vinylcyclohexene oxide and 2.0 g1,1,3,3-tetramethyldisiloxane and mixed. The solution was stirred at 85°C. for 1.5 hours, resulting in the formation of selective hydrosilationproduct (1,3-bis[2-(3{7-oxabicyclo[4.1.0]heptyl}ethyl]-tetramethyldisiloxane) without any polymer formation.This was confirmed by NMR and GPC analyses.

Example 9

A. There were reacted in 50 mL toluene with stirring at 85° C. for 30hours, 0.20 g of (n-Bu)₄ NBr, 20.0 mg of rhodium trichloride hydrate. Abrown oily product was obtained at the bottom of the reaction vesselwhich was used as hydrosilation catalyst.

B. The procedure of 8B was followed to test the catalyst selectivity. Nopolymerization was observed.

C. The procedure of 8C was followed to test the catalyst hydrosilationselectivity. The selective hydrosilation product (1,3-bis [2-(3{7-oxabicyclo [4.1.0 ]heptyl}ethyl]-tetramethyldisiloxane) was againobtained without any polymer formation.

It is understood that various other modifications will be apparent toand can be readily; made by those skilled in the art without departingfrom the scope and spirit of the present invention. Accordingly, it isnot intended that the scope of the claims appended hereto be limited tothe description set forth above but rather that the claims be construedas encompassing all of the features of patentable novelty which residein the present invention, including all features which would be treatedas equivalents thereof by those skilled in the art to which theinvention pertains.

What is claimed is:
 1. A method for making an epoxy-containingorganosilicone compound, comprising the steps of:(i) preparing themixture comprising:(A) from about 1 to about 10 parts by weight of thecomposition of an ethylenically unsaturated epoxide; (B) from about 0.5to about 400 parts by weight of the composition of anorganohydrogensiloxane or an organohydrogensilane; based on A and (C)from about 1 to about 5000 parts per million by weight as compared tothe weight of the composition of a hydrosilation catalyst of the formula

    [R.sub.4 M].sup.+ [RhCl.sub.3 Br].sup.-

wherein M is phosphorous or nitrogen and R is an organic radicalcomprising C₁₋₁₈, substituted or unsubstituted, linear alkyl radical, oran aryl, alkaryl or aralkyl radical; and (ii) reacting the mixture ofsaid step (i), at a temperature of from about 0° to about 200° whichpromote a hydrosilation addition reaction between (A) and (B) to producean epoxysilicone product, and which do not promote an epoxidering-opening reaction in either (A) or in said epoxysilicone product. 2.The method as set forth in claim 1 wherein Component (A) is a aliphatic(glycidyl) or cycloaliphatic epoxy compound.
 3. The method as set forthin claim 2 wherein Component (A) is selected from the group consistingof allyl glycidyl ether; methallyl glycidyl ether;1-methyl-4-isopropenyl cyclohexene oxide;2,6-dimethyl-2,3-epoxy-7-octene; 1,4-dimethyl-4-vinylcyclohexene oxide;4-vinylcyclohexene oxide; vinylnorbornene monoxide; dicyclopentadienemonoxide; 1,2-epoxy-6-heptene; and 1,2-epoxy-3-butene.
 4. The method asset forth in claim 1 wherein Component (B) is a linear hydrogensubstituted polysiloxane or silane, or a cyclic hydrogen substitutedpolysiloxane or silane, or a combination of the two.
 5. The method asset forth in claim 4 wherein Component (B) is selected from the groupconsisting of 1,1,3,3-tetraalkyldisiloxane,dialkylhydrogensiloxy-endstopped polydialkylsiloxane,1,1,3,3tetramethyldisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane,methyldimethoxysilane, triethylsilane, and methyldiethoxysilane.
 6. Themethod set forth in claim 1 wherein the said rhodium containingselective hydrosilation catalyst is selected from the group consistingof

    [(n-C.sub.4 H.sub.9).sub.4 N].sup.+ [RhCl.sub.3 Br].sup.- ; [(n-C.sub.4 H.sub.9).sub.4 P].sup.+ [RhCl.sub.3 Br].sup.- ;

    [(n-C.sub.18 H.sub.37 ).sub.4 N].sup.+ [RhCl.sub.3 Br].sup.- ; and [(n-C.sub.7 H.sub.15).sub.4 N].sup.+ [RhCl.sub.3 Br].sup.-.


7. The method as set forth in claim 1, wherein step (ii) comprisesreacting the mixture of said step (i) at a temperature of from about 25°to about 150° C.
 8. A method of suppressing oxirane ring-openingpolymerization during a hydrosilation addition reaction between anethylenically unsaturated epoxide and an organohydrogensilane ororganohydrogensiloxane comprising the steps:(i) providing a mixturecomprising an ethylenically unsaturated epoxide, an organohydrogensilaneor organohydrogensiloxane and a rhodium containing selectivehydrosilation catalyst; and (ii) reacting the mixture of said step (i)at a temperature of from about 0° to about 200° C. which promote thehydrosilation addition reaction between said ethylenically unsaturatedepoxide and said organohydrogensilane or organohydrogensiloxane but doesnot promote the epoxide ring-opening polymerization reaction of eithersaid ethylenically unsaturated epoxide or said epoxysilicone product. 9.The method as set forth in claim 8, wherein step (ii) comprises reactingthe mixture of said step (i) at a temperature of from about 25° to about150° C.